JP2014205650A - Hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair cosmetic having both fixation ability and arrangement ability and capable of eliminating the need for admixing alcohol or achieving considerable reduction of alcohol.SOLUTION: A hair cosmetic contains a viscosity setting resin consisting of (A) a nonionic monofunctional ethylenic unsaturated monomer with the glass-transition temperature of the homopolymer being 300 K (27°C) or less, (B) an ethylenically unsaturated monomer having at least one carboxyl group in a molecule, and (C) a bifunctional ethylenically unsaturated monomer represented by the formula [I].

Description

  The present invention relates to a hair cosmetic that has an excellent fixing force and arrangement force (including re-styling force), and that can reduce discomfort and safety problems caused by alcohol. More specifically, by using a novel polymer with high water solubility as a polymer for fixing and re-hairing hair, it is not necessary to add alcohol to dissolve the polymer, or the amount of alcohol to be added The present invention relates to a hair cosmetic that can significantly reduce hair.

  Hair styling includes two functions: creating a hairstyle and retaining the created hairstyle. The principle of exerting these two functions is said to be fixation and adhesion (Non-Patent Document 1).

  However, in hair styling by sticking, a film forming agent (polymer resin) called a set agent forms a hard film, so it is impossible to re-hair from a hairstyle once made, and if the film is broken, the hair styling function is lost. There were drawbacks. That is, the styling agent based on fixing with the set resin has a problem that it is excellent in fixing the hairstyle but has poor arranging power.

  On the other hand, the styling based on adhesion has a feature that it can be re-styled through a finger or a brush because the adhesive oily component maintains fluidity and adhesion on the hair. For this reason, although it was excellent in what is called arrangement power, there was a problem that fixing power (keep power) like hair cosmetics using set resin was not obtained.

  Therefore, in recent years, attention has been focused on hair cosmetics that can fix hair (hair style) and at the same time re-hair after fixing. Among them, it has been proposed to blend a special polymer having moderate hardness and high adhesive strength when forming a film. For example, Patent Document 1 discloses a hair cosmetic containing an adhesive set resin obtained by polymerizing predetermined monomers A to D, alcohol, and water. Patent Document 2 includes a copolymer of a monofunctional ethylenically unsaturated monomer component (A) and a polyfunctional ethylenically unsaturated monomer component (B). A base for hair cosmetics characterized by having a glass transition temperature calculated theoretically from the composition of 40 ° C. or less and having solvent solubility is disclosed.

  The adhesive set resins or hair cosmetic bases described in Patent Documents 1 and 2 are said to have a fixing force and an arranging force, thereby achieving both hairstyle retention and re-styling. . However, these adhesive set resins or hair cosmetic bases are all highly soluble in alcohol, but have low water solubility and are difficult to dissolve stably and transparently in aqueous solvents. Therefore, in order to mix these with hair cosmetics, it is necessary to highly blend alcohols such as ethanol which are usually used in cosmetics and solubilize them in an aqueous medium. However, alcohols have a unique odor, irritate the skin, and may cause rough skin or allergies depending on the skin quality. In addition, since it is highly volatile and easily flammable, it must be handled with care, such as avoiding fire. Furthermore, there are many cosmetic raw materials that are not suitable for use in combination with alcohols, such as preventing the thickening effect of thickeners such as carbomers, or reducing the activity of water-soluble extracts and water-soluble drugs.

"Development of functional cosmetics II", supervised by Masato Suzuki, published by CMC Publishing, 1996, Chapter 10 Functions and latest technology of hairdressing agents

Japanese Patent No. 5108817 JP 2011-26250 A

  The present invention has been made in view of the drawbacks of the prior art described above, and eliminates the need for blending alcohols while achieving both hairstyle fixing force and arranging power (including re-styling power), or It aims at providing the hair cosmetics which can reduce the compounding quantity of alcohol significantly.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a new highly hydrophilic adhesive set resin obtained by polymerizing a specific monomer at a specific ratio. Thus, the present inventors have found that a hair cosmetic that does not require high blending of alcohols for solubilization as in the prior art, while having both fixing force and arranging power, has been completed.

That is, the present invention provides the following monomers (A), (B), and (C):
(A) 71 to 91 weights of a nonionic monofunctional ethylenically unsaturated monomer (hereinafter referred to as “monomer A”) having a glass transition temperature of 300 K (27 ° C.) or less of a homopolymer obtained by polymerization %,
(B) 4 to 14 wt% of an ethylenically unsaturated monomer having at least one carboxyl group in the molecule (hereinafter referred to as “monomer B”), and (C) the following formula [I]:
Wherein R ₁ and R ₂ are H or CH ₃ , X is an oxyethylene group (EO), oxypropylene group (PO), oxybutylene group (BO), and n is an integer of 1-100. is there)
5 to 15% by weight of a bifunctional ethylenically unsaturated monomer (hereinafter referred to as “monomer C”) represented by
The gist of the present invention is an adhesive set resin obtained by polymerizing the hair and a hair cosmetic containing water.

  The hair cosmetic composition according to the present invention uses a highly water-soluble adhesive set resin obtained by polymerizing a specific monomer at a specific ratio. Can be dissolved stably. For this reason, it is not necessary to mix | blend alcohols highly as a solubilizing agent conventionally, and the problem of the discomfort and safety resulting from alcohol can be avoided. In addition, since it is possible to add a component that is difficult to use in combination with alcohols, the range of hair cosmetic preparations can be expanded.

  The hair cosmetic composition of the present invention comprises an adhesive set resin obtained by polymerizing the monomer A, the monomer B, and the monomer C at a predetermined ratio, and water. To do. Hereinafter, the present invention will be described in detail.

<Adhesive set resin>
The adhesive set resin blended in the hair cosmetic composition of the present invention can be obtained by polymerizing the following monomer A, monomer B, and monomer C at a predetermined ratio.

[Monomer A]
Monomer A constituting the adhesive set resin is a nonionic monofunctional ethylenically unsaturated monomer having a glass transition temperature of 300 K (27 ° C.) or less when polymerized alone to form a homopolymer. If the homopolymer is a monomer that satisfies the glass transition temperature, one type of monomer can be used alone, or two or more types of monomers can be used in combination. On the other hand, when a monomer whose glass transition temperature of the homopolymer is outside the above range is used in combination, the adhesiveness is lowered and the arranging power is inferior, and the finish tends to be hard and crumpled, and the effect of the present invention cannot be obtained.

  When each monomer A is a homopolymer, the glass transition temperature is 300K (27 ° C) or lower, more preferably 270K (-3 ° C) or lower, and further preferably 260K (-13 ° C) or lower. . When the glass transition temperature is 300 K (27 ° C.) or less, the hair styling property of the hair cosmetic containing the adhesive set resin is excellent. The glass transition temperature of the monomer homopolymer can be measured by a general method such as DSC (Differential Scanning Calorimetry), and the values described in publications such as handbooks can also be adopted. .

  Examples of the main nonionic monofunctional ethylenically unsaturated monomer satisfying the glass transition temperature include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl (meth) acrylate, isobutyl acrylate, acrylic Isoamyl acid, 2-ethylhexyl (meth) acrylate, cyclohexyl acrylate, isooctyl acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters of alcohols having linear, branched or alicyclic hydrocarbon groups such as tridecyl, myristyl (meth) acrylate, palmityl methacrylate, etc .; 2-hydroxyethyl acrylate, ( (Meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid (Meth) acrylic acid hydroxyalkyl ester such as 4-hydroxybutyl; (meth) acrylic acid alkoxyalkyl ester such as (meth) acrylic acid methoxyethyl, (meth) acrylic acid ethoxyethyl; polyethylene glycol mono (meth) acrylate, Monoesters of polyalkylene glycol and (meth) acrylic acid, such as polypropylene glycol mono (meth) acrylate; Monoesters of polyalkylene glycol and (meth) acrylic acid, such as methoxypolyethylene glycol mono (meth) acrylate And monofunctional unsaturated monomers such as benzyl acrylate and phenoxyethyl acrylate. These monomers can be used singly or in combination of two or more.

  The blending ratio of the monomer A is 71 to 91% by weight, more preferably 75 to 87% by weight, based on the adhesive set resin. When the blending ratio of the monomer A is less than 71% by weight, the tackiness tends to decrease, and when it exceeds 91% by weight, the water solubility and the fixing force tend to decrease.

[Monomer B]
The monomer B constituting the adhesive set resin is an ethylenically unsaturated monomer having at least one carboxyl group in the molecule. A typical example is a vinyl-based monomer having at least one carboxyl group (may be an anhydride-formed form) in one molecule.
Specific examples of the monomer B include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, maleic anhydride, and citraconic acid; Monoalkyl esters of unsaturated dicarboxylic acids such as acid monoalkyl esters, fumaric acid monoalkyl esters, itaconic acid monoalkyl esters, 2-methacryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, β-carboxy Ethyl acrylate; acryloyloxyethyl succinate, 2-propenoic acid, 3- (2-carboxyethoxy) -3-oxypropyl ester, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid, 2- (meth) acryloyloxy Ethyl hexahydro Like barrel acid. These monomers can be used singly or in combination of two or more.

  Especially, since the high water solubility can be provided to adhesive set resin, it is preferable that the monomer B is 1 type or 2 types selected from acrylic acid and methacrylic acid.

  The blending ratio of the monomer B is 4 to 14% by weight, more preferably 5 to 10% by weight with respect to the adhesive set resin. If the blending ratio of the monomer B is less than 4% by weight, the water solubility tends to decrease, and if it exceeds 14% by weight, the tackiness tends to decrease and the hair style keeping power tends to be inferior.

[Monomer C]
The monomer C constituting the adhesive set resin is represented by the following formula [I]:
Wherein R ₁ and R ₂ are H or CH ₃ , X is an oxyethylene group (EO), oxypropylene group (PO), oxybutylene group (BO), and n is an integer of 1-100. is there)
Is a bifunctional ethylenically unsaturated monomer represented by

  Examples of the monomer C include PEG (n = 23) diacrylate, PEG (n = 9) diacrylate, PEG (n = 6) diacrylate, PEG (n = 3) diacrylate, and the like. . These monomers can be used singly or in combination of two or more.

  The blending ratio of the monomer C is 5 to 15% by weight, more preferably 5 to 10% by weight, based on the adhesive set resin. When the blending ratio of the monomer C is less than 5% by weight, the tackiness is inferior and the finish tends to be hard, and when it exceeds 15% by weight, the film formability is lowered and the hairstyle fixing force tends to be inferior. There is.

  The weight average molecular weight of the adhesive set resin is in the range of 1,000 to 1,000,000, preferably in the range of 10,000 to 500,000, and more preferably in the range of 40,000 to 300,000. If the weight average molecular weight is 1000 or more, an effect excellent in fixing and re-styling hairstyles can be exhibited. If the weight average molecular weight is 1000000 or less, the hair cosmetic containing the adhesive set resin is hair. Even if it is a spray form such as a spray, a good spray is possible.

  The adhesive set resin used in the hair cosmetic composition of the present invention is prepared by mixing the above monomers A, B and C in the above ratio, and polymerizing using a standard method in an appropriate solvent as necessary. It can be prepared by reacting. For example, it can be obtained by thermal polymerization in ethanol at about 80 ° C. for 8 hours using a polymerization initiator such as 2,2′-azobisisobutyronitrile in ethanol. The obtained polymer can be appropriately purified and used.

  The blending amount of the adhesive set resin in the hair cosmetic composition of the present invention may vary depending on the product form, but is generally 0.1 to 30% by weight, preferably 1 to 20% by weight, more preferably 2 to 15% by weight. If it is less than 0.1% by weight, the arranging power may be insufficient, and if it exceeds 30% by weight, hair may become stiff.

<Water>
The hair cosmetic composition of the present invention contains water in addition to the above-mentioned adhesive set resin. The water used in the present invention is not particularly limited, and specific examples thereof include purified water and ion exchange water.
Although the compounding quantity of water may change according to the product form, generally 5 to 95 weight% is preferable with respect to the hair cosmetics whole quantity, More preferably, it is 20 to 80 weight%. Usability etc. may fall that the compounding quantity of water is outside the said range.

  Since the hair cosmetic composition of the present invention uses the above-mentioned adhesive set resin having high water solubility, the blending amount of alcohols such as ethanol conventionally blended for dissolving the resin is reduced or eliminated. be able to. However, if necessary, alcohols generally used in cosmetics may be blended for the purpose of improving the quick drying property and usability of hair cosmetics. When alcohols are blended in the hair cosmetic composition of the present invention, it is preferably 30% by weight or less, more preferably 10% by weight or less, based on the total amount of the hair cosmetic product, in order to suppress discomfort caused by alcohol. .

  Since the hair cosmetic composition of the present invention can reduce or eliminate the blending amount of alcohols such as ethanol as described above, it uses a raw material that is incompatible with alcohols that are not effective when used in combination with alcohols. It is especially suitable for

  Furthermore, the hair cosmetic composition of the present invention preferably contains at least one selected from sugars, sugar alcohols, and EO / PO derivatives. By blending these, the ability to arrange can be further improved. .

  Examples of the sugar used in the present invention include monosaccharides and oligosaccharides. Specifically, monosaccharides include three carbon sugars (for example, D-glyceryl aldehyde, dihydroxyacetone, etc.); four carbon sugars (for example, D-erythrose, D-erythrulose, D-threose, etc.); For example, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc .; hexose (eg, D-glucose, D-talose, D-bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); heptacarbon (eg, aldheptose, heproose, etc.); octose (eg, octulose, etc.); (For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose Amino sugar (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.); uronic acid (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturon) Acid, L-iduronic acid, etc.). In addition, derivatives thereof (POE / POP addition, alkyl group addition, cationization, anionization, silylation) and the like can be mentioned.

  Examples of oligosaccharides include sucrose, maltose, cellobiose, gunthianos, umbelliferose, lactose, planteose, isolicnose, trehalose, raffinose, lycnose, umbilicin, stachyose verbus course and the like. In addition, derivatives thereof (POE / POP addition, alkyl group addition, cationization, anionization, silylation) and the like can be mentioned.

Examples of the sugar alcohol include mannitol, xylitol, erythritol, sorbitol, maltitol, inositol and the like. These derivatives (POE and / or POP adduct, alkyl group adduct, cationized product, anionized product, silylated product) and the like can also be used.
The sugar and sugar alcohol used in the present invention are not limited. Among them, sugar alcohols, particularly maltitol and sorbitol are most suitable.

  The blending amount of sugar and / or sugar alcohol in the hair cosmetic composition of the present invention is generally 0.1 to 20% by weight, preferably 1 to 20% by weight, more preferably 3 to 10% by weight. If it is less than 0.1% by weight, the effect of improving the arranging power (re-hair-setting ability) may not be sufficient, and if it exceeds 30% by weight, stickiness may occur.

The EO / PO derivatives used in the present invention are compounds including the following hair styling oil and polyalkylene glycols.
The hair styling oil means an EO / PO adduct of monovalent to tetravalent alcohol or monovalent to trivalent carboxylic acid. Commercially available products can be used, for example, Unilube 50 MB 168, Unilube MB370, Berthamol P-700, Berthamol DG-25, Triol G-40, Sabondol SGP-7, Sabondol GP-9 (or more NOF Corporation) Este Mall 50 (Nisshin Oillio Group Co., Ltd.).

The polyalkylene glycol means a polyalkylene glycol, for example, an addition polymer of ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO). Commercially available products can be used, for example, EO addition polymers: PEG200, PEG300, PEG400, PEG600, PEG1000, PEG1540, PEG2000, PEG4000, PEG6000, PEG11000, PEG20000 (NOF Corporation or Toho Chemical Industry Co., Ltd.) PO addition polymer: Uniol D-700, Uniol D-1000, Uniol D-1200, Uniol D-2000 (above NOF Corporation), etc. can be mentioned.
The polyalkylene glycols used in the present invention are not limited, but among them, polyethylene glycol is most suitable.

  The blending amount of the EO / PO derivative in the hair cosmetic composition of the present invention is generally 0.1 to 20% by weight, preferably 1 to 20% by weight, more preferably 3 to 10% by weight. If it is less than 0.1% by weight, the effect of improving the arranging power (re-hair-setting ability) may not be sufficient, and if it exceeds 30% by weight, stickiness may occur.

  The hair cosmetic composition of the present invention can be provided in various forms such as a hair liquid, a hair foam, a hair mousse, a hair spray, a hair mist, a hair gel, and a hair wax.

  For example, according to the form of the hair cosmetic of the present invention, other components conventionally used in hair cosmetics may be blended within a range that does not impair the effects of the present invention. For example, surfactants, conditioning agents, thickeners, viscosity modifiers, sequestering agents, UV absorbers, antioxidants, preservatives, powder components, antidandruff agents, hair restorers, pH adjusters, dyes, 1 type, or 2 or more types, such as a fragrance | flavor, can be mix | blended suitably in the range which does not impair the effect of this invention.

  Hereinafter, the present invention will be described in more detail with specific examples, but the present invention is not limited to the following examples. Moreover, unless otherwise indicated, the compounding quantity in a following example etc. shows weight%.

(Production example and comparative production example)
Polymerization is performed with the monomer composition shown in Table 1 below, and the adhesive set resin of the present invention (Production Examples 1 to 4) and the adhesive set resin that does not satisfy the requirements of the present invention (Comparative Production Examples 1 to 5) Prepared.
Specifically, a mixture in which 100 parts of monomers were mixed was prepared in advance, and a dropping funnel containing this mixture, a reflux condenser, a thermometer, a nitrogen replacement tube, and a 1 L capacity equipped with a stirrer were attached. A five-necked flask was charged with 100 parts of ethanol, heated in a nitrogen stream, and brought to a reflux state (about 80 ° C.). In this ethanol, a polymerization initiator (2,2′-azobisisobutyro was added). 1 part of nitrile) was added and the mixture was added dropwise continuously for 2 hours. Thereafter, the polymerization reaction was allowed to proceed in a reflux state for 8 hours. Next, the solvent content of this solution was adjusted by distilling off the solvent from the solution in the five-necked flask and adding ethanol to obtain a solution of a hair cosmetic base having a solid content concentration of 50%.

(Examples and Comparative Examples)
Samples are prepared using the resins of the above production examples and comparative production examples, and the solubility (transparency), fixing force, adhesive strength, arranging power, re-hair styling power, hairiness, and hair when using the samples. The sense of bundle was evaluated. The evaluation method and evaluation criteria for each characteristic are as follows.

1. Solubility (transparency)
After mixing 5% by weight of the resin of the above production example and the comparative production example with 95% by weight of water and stirring with a stirrer at room temperature for 5 minutes, the transparency of the mixed solution was visually evaluated.

<Evaluation criteria>
◎: Pretty transparent ○: Slightly transparent △: Slightly turbid ×: Slightly turbid

2. Fixing strength 0.5 g of a sample was applied to one bundle of black virgin hair (length: 20 cm, mass: 2 g), and the hair bundle after drying at room temperature was evaluated by a sensory test.

<Evaluation criteria>
◎: Feels quite firm ○: Feels somewhat firm △: Feels slightly firm ×: Does not feel firm

3. Adhesive strength 0.5 g of the sample was applied to one bundle of black virgin hair (length 20 cm, mass 2 g), and the adhesive strength on the hair was evaluated by a sensory test for the hair bundle after drying at room temperature.

<Evaluation criteria>
◎: Feels quite sticky ○: Feels slightly sticky △: Feels slightly sticky ×: Does not feel sticky

4). Arrangement force 0.5 g of a sample was applied to a bundle of black virgin hair (length 20 cm, mass 2 g), and the ease of arrangement when pinching the hair and twisting it was evaluated by a sensory test.

<Evaluation criteria>
◎: Arrangement is fairly easy ○: Arrangement is somewhat easy △: Difficult to arrange × ×: Difficult to arrange

5. Re-styling power 0.5g of sample is applied to a bundle of black virgin hair (length: 20cm, mass: 2g), and hair is straightened immediately after application. Was evaluated by a sensory test.

<Evaluation criteria>
◎: There is considerable hair styling ability ○: There is some hair styling ability △: There is little hair styling ability ×: There is no hair styling ability

6). No puffiness A 0.5 g sample was applied to a bundle of black virgin hair (length 20 cm, mass 2 g), and the hair bundle after drying at room temperature was evaluated by sensory test. did.

<Evaluation criteria>
◎: Not quite crisp ○: Slightly not △: Slightly crumbly ×: Pussy

7). Hair bundle feeling After applying 0.5 g of a sample to a bundle of black virgin hair (length 20 cm, mass 2 g) and drying it at room temperature, the hair bundle is formed by pinching and twisting to adjust the hair. Ease was evaluated by a sensory test.

<Evaluation criteria>
◎: Hair bundle is easily formed ○: Hair bundle is slightly formed △: Hair bundle is slightly difficult ×: Hair bundle is hardly formed

Samples having the compositions listed in Table 2 below were prepared. The sample was prepared by adding each polymer to a mixture of water and ethanol and stirring. The characteristics of each sample were then evaluated according to the above criteria. The results are also shown in Table 2.

  As is clear from the results shown in Table 2, when the adhesive set resin obtained using a nonionic monofunctional ethylenically unsaturated monomer having a glass transition temperature exceeding 300 K (27 ° C.) is blended (comparison) Example 1), when monomer B exceeds 14% by weight (Comparative Example 2), when monomer C is outside the range of 5 to 15% by weight (Comparative Examples 4 and 5), Arrangement power, re-hair styling, crispness, and hair bundle feeling were all poor. Further, in Comparative Example 4 in which the monomer C exceeds 15% by weight, the fixing force was further insufficient. On the other hand, when the monomer B is less than 4% by weight (Comparative Example 3), the adhesive strength, the arranging power, the hair styling property, the crispness, and the hair bundle feeling are sufficient, but the solubility and the fixing strength are inferior. It was. On the other hand, Examples 1-4 which mix | blended the adhesive set resin of this invention showed the result excellent in all the evaluation items.

Claims (2)

Monomers (A), (B), and (C) shown below:
(A) 71 to 91% by weight of a nonionic monofunctional ethylenically unsaturated monomer having a glass transition temperature of 300K (27 ° C.) or less of a homopolymer obtained by polymerization,
(B) 4 to 14% by weight of an ethylenically unsaturated monomer having at least one carboxyl group in the molecule, and (C) the following formula [I]:
Wherein R ₁ and R ₂ are H or CH ₃ , X is an oxyethylene group (EO), oxypropylene group (PO), oxybutylene group (BO), and n is an integer of 1-100. is there)
5 to 15% by weight of a bifunctional ethylenically unsaturated monomer represented by
A hair cosmetic composition comprising an adhesive set resin obtained by polymerizing a water and water.   (B) The hair cosmetic according to claim 1, wherein the ethylenically unsaturated monomer having at least one carboxyl group in the molecule is one or two selected from acrylic acid and methacrylic acid.